A sterilization combination and its application

Abstract

The present invention belongs to the technical field of sterilization, and discloses a sterilization composition and its application, wherein the active ingredients of the sterilization composition include tetrazolium pyridine and a compound of formula I: the mass ratio of the tetrazolium pyridine to the compound of formula I is 1:20 to 30:1. The composition of the present invention has a synergistic effect on a variety of plant pathogens, can significantly reduce the dosage, and is safe for crops and non-target organisms.

Description

Technical Field

[0001] The present invention belongs to the technical field of sterilization, and in particular relates to a sterilization composition and application thereof. Background Art

[0002] Picarbutrazox, internationally known as picarbutrazox, CAS registration number: 500207-04-5, is a carbamate fungicide developed by Japan Soda Co., Ltd. Its mechanism of action is to inhibit the formation of bacterial cell membranes, inhibit hyphae growth and spore germination, reduce sporangium formation and the number of zoospores, and can prevent and control oomycete diseases such as downy mildew and blight.

[0003] The compound of Formula I is a novel substituted aniline broad-spectrum fungicide developed by Ishihara Co., Ltd. of Japan. Its unique mechanism of action, capable of uncoupling mitochondrial oxidative phosphorylation, offers high efficacy and broad-spectrum properties. It effectively inhibits the germination of spores and mycelial growth of various plant pathogens, particularly strongly inhibiting the release and germination of zoospores. It is particularly effective against various gray molds caused by Botrytis cinerea. It also exhibits good activity against diseases caused by pathogens such as Alternaria, Phytophthora, Monoparagus, Sclerotinia, and Venturia. Its structural formula is as follows:

[0004]

[0005] In order to effectively control the harm of pathogens, chemical control has always been the main mode of agricultural production. However, most of the control agents are single agents, and long-term use can easily make pathogens develop drug resistance, thereby unable to achieve control effects. Therefore, using compounded agents has become an important research on the chemical control of plant diseases, screening out efficient and economical compounded agents, which is of great significance to the healthy development of agriculture. The inventors have carried out a large number of experimental studies and found that tetrazolium pyrrolidone and formula I compound are compounded, within a certain range, to plant multiple pathogens with obvious synergistic effect, reducing the use dose of the agent, and reducing the agent residues in agricultural products. Summary of the Invention

[0006] Based on the above situation, the purpose of the present invention is to provide a fungicide composition and its preparation, which has good prevention and control effects on various plant diseases, can effectively control the development of drug resistance in pathogenic microorganisms, reduce the amount of drugs used, reduce the cost of drugs, and is environmentally friendly.

[0007] In order to achieve the above object, the present invention adopts the following technical solution: a fungicide composition, wherein the active ingredients of the fungicide composition include tetrazolium pyrrolidone and a compound of formula I:

[0008] Furthermore, the mass ratio of the tetrazolium pyrrolidone to the compound of formula I is 1:20 to 30:1;

[0009] Furthermore, the mass ratio of tetrazolium pyrrolidone to the compound of formula I is 1:20, 1:10, 1:5, 1:1, 3:2, 2:1, 3:1, 5:1, 10:1, and 30:1;

[0010] Furthermore, the mass ratio of the tetrazolium pyrrolidone to the compound of formula I is 1:10 to 10:1;

[0011] Furthermore, the mass ratio of tetrazolium pyrrolidone to the compound of formula I is 1:10, 1:5, 1:1, 3:2, 2:1, 3:1, 5:1, 10:1;

[0012] Furthermore, the mass ratio of the active ingredient tetrazolium pyrrolidone to the compound of formula I in the fungicidal composition is 1:20, 1:10, 1:5, 1:1, 3:2, 3:1, 5:1, 10:1, and 30:1, and when controlling potato late blight, the combined action type is synergistic;

[0013] When the fungicidal composition is used to control potato late blight, the preferred mass ratio of the active ingredient tetrazolium pyrrolidone to the compound of formula I is 1:20 to 30:1;

[0014] Furthermore, the mass ratio of the active ingredient tetrazolium pyrrolidone to the compound of formula I in the fungicidal composition is 1:10, 1:5, 1:1, 2:1, 3:1, 5:1, and 10:1, and when controlling cucumber downy mildew, the combined action type is synergistic;

[0015] When the bactericidal composition is used to control cucumber downy mildew, the preferred mass ratio of the active ingredient tetrazolium pyrrolidone to the compound of formula I is 1:10 to 10:1;

[0016] Furthermore, the total weight of the bactericidal composition is 100 wt%, and the total weight of the active ingredient tetrazolium pyrrolidone and the compound of formula I accounts for 0.1% to 90% of the total weight of the bactericidal composition;

[0017] Furthermore, the total weight of the fungicide composition is 100 wt%, and the total weight of the active ingredient tetrazolium pyrrolidone and the compound of formula I accounts for 2% to 70% of the total weight of the fungicide composition;

[0018] Furthermore, the fungicide composition further comprises, in addition to the active ingredient, agriculturally acceptable auxiliary ingredients, wherein the auxiliary ingredients are selected from one or more of a wetting agent, a dispersant, an emulsifier, a thickener, a disintegrant, an antifreeze agent, a defoaming agent, a solvent, a preservative, a stabilizer, a synergist or a carrier;

[0019] Furthermore, the wetting agent is selected from a mixture of one or more of sodium lauryl sulfate, sodium dodecylbenzene sulfonate, lakai powder BX, wetting and penetrating agent F, saponin powder, silkworm excrement or soapberry powder;

[0020] Furthermore, the dispersant is selected from a mixture of one or more of polycarboxylates, lignin sulfonates, alkylphenol polyoxyethylene ether formaldehyde condensate sulfates, alkylbenzene sulfonate calcium, naphthalenesulfonic acid formaldehyde condensate sodium salts, alkylphenol polyoxyethylene ethers, fatty amine polyoxyethylene ethers, fatty acid polyoxyethylene ethers or glycerol fatty acid ester polyoxyethylene ethers;

[0021] Furthermore, the emulsifier is selected from one or more of alkylbenzene sulfonate, OP series phosphate (octylphenol polyoxyethylene ether phosphate), phenylphenol polyoxyethylene ether phosphate, styrene polyoxyethylene ether ammonium sulfate, alkyl biphenyl ether disulfonic acid magnesium salt, triethanolamine salt, benzyl dimethylphenol polyoxyethyl ether, alkylphenol formaldehyde resin polyoxyethyl ether, phenethylphenol formaldehyde resin polyoxyethyl ether, phenethylphenol polyoxyethyl polypropylene ether, ethylene oxide-propylene oxide block copolymer, OP series (octylphenol polyoxyethylene ether), castor oil polyoxyethylene ether, alkylaryl polyoxyethylene polyoxypropylene ether, sorbitan monostearate, sorbitan fatty acid ester polyoxyethylene ether or fatty alcohol polyoxyethylene ether;

[0022] Furthermore, the thickener is selected from a mixture of one or more of xanthan gum, polyvinyl alcohol, bentonite, carboxymethyl cellulose or magnesium aluminum silicate;

[0023] Furthermore, the disintegrant is selected from a mixture of one or more of bentonite, urea, ammonium sulfate, aluminum chloride, low-substituted hydroxypropyl cellulose, lactose, citric acid, succinic acid or sodium bicarbonate;

[0024] Furthermore, the antifreeze agent is selected from a mixture of one or more of ethylene glycol, propylene glycol, glycerol or urea;

[0025] Furthermore, the defoaming agent is selected from silicone oil, silicone compounds, C 10 ~C 20 Saturated fatty acid compounds or C8~C 10 A mixture of one or more fatty alcohol compounds;

[0026] Furthermore, the solvent is selected from a mixture of one or more of N,N-dimethylformamide, cyclohexanone, butyl ether, xylene, dimethyl sulfoxide, methanol, ethylene glycol, ethanol, propanol, butanol, trimethylcyclohexanone, N-octyl pyrrolidone, toluene, ethanolamine, triethanolamine, isopropylamine, N-methyl pyrrolidone, diethylene glycol, ethylene glycol methyl ether, ethyl acetate or acetonitrile;

[0027] Furthermore, the stabilizer is selected from a mixture of one or more of epoxy soybean oil, epichlorohydrin, BHT, ethyl acetate, and triphenyl phosphate;

[0028] Furthermore, the penetrant is selected from a mixture of one or more of penetrant JFC, penetrant T, azone or silicone;

[0029] Furthermore, the carrier is one, two or three of a solvent or a filler, and water is preferably deionized water;

[0030] Furthermore, the filler is selected from a mixture of one or more of kaolin, diatomaceous earth, bentonite, attapulgite, white carbon black, starch or light calcium carbonate;

[0031] The above substances can be obtained commercially;

[0032] The fungicidal composition of the present invention can be prepared into any formulation permitted in agriculture as required;

[0033] Furthermore, the formulation is in the form of a solid preparation, a liquid preparation and / or a seed treatment preparation;

[0034] Furthermore, the solid preparation is a direct-use solid preparation, a dispersible solid preparation or a soluble solid preparation;

[0035] Furthermore, the directly-used solid preparation is a powder, granule, pellet, tablet or strip;

[0036] The dispersible solid preparation is a wettable powder, an oil-dispersible powder, an emulsion powder, a water-dispersible granule, an emulsion granule or a water-dispersible tablet;

[0037] The soluble solid preparation is a soluble powder, a soluble tablet or a soluble granule;

[0038] Furthermore, the liquid preparation is a solution preparation, a dispersed liquid preparation, an emulsion preparation, a suspension preparation or a multiphase preparation;

[0039] Furthermore, the solution preparation is a soluble solution, a soluble gel, an oil or a film-spreading oil;

[0040] The dispersed liquid preparation is an emulsifiable concentrate, latex, dispersible liquid or ointment;

[0041] The emulsion preparation is a water emulsion, an oil emulsion, a microemulsion or a fat preparation;

[0042] The suspension preparation is a suspension concentrate, a microcapsule suspension concentrate, an oil suspension concentrate or a dispersible oil suspension concentrate;

[0043] The multiphase preparation is a suspoemulsion, a microcapsule suspension-suspension concentrate, a microcapsule suspension-water emulsion or a microcapsule suspension-suspoemulsion;

[0044] Furthermore, the seed treatment formulation includes a seed treatment solid formulation or a seed treatment liquid formulation;

[0045] Furthermore, the seed treatment solid preparation is a seed treatment dry powder or a seed treatment dispersible powder;

[0046] The seed treatment liquid preparation is a seed treatment liquid, a seed treatment emulsion and / or a seed treatment suspension;

[0047] Furthermore, the solid preparation is a water-dispersible granule and / or a wettable powder, and the liquid preparation is a suspension.

[0048] The present invention also discloses the use of the above-mentioned fungicide composition and / or its preparation in preventing and controlling plant diseases.

[0049] Furthermore, the plant disease is caused by one or more of the following pathogens: Mastigomycotina, Zygomycotina, Ascomycotina, Basidiomycotina and / or Deuteromycotina fungi;

[0050] Furthermore, the plant disease is caused by fungi of the subphylum Mastigomycotina;

[0051] Furthermore, the Mastigomycotina fungus is Phytophthora infestans and / or Pseudocoperonospora cubana;

[0052] Furthermore, the bactericidal composition and / or its preparation is applied to the pathogens to be controlled or their growth medium at an effective dose.

[0053] The beneficial effects of the present invention are as follows:

[0054] 1) The present invention rationally mixes two compounds with different mechanisms of action, thereby expanding the control range of the agent, improving the control effect and extending the control time;

[0055] 2) Prevent or delay the development of drug resistance in pathogens and extend the service life of pesticides;

[0056] 3) Reduce the dosage of pesticides, be friendly to the environment, safe for crops, and reduce the pesticide residues in agricultural and sideline products. DETAILED DESCRIPTION

[0057] In order to make the technical solutions, objectives and advantages of the present invention more clearly understood, the present invention is described with reference to the following specific embodiments. However, the present invention can be implemented in various forms and should not be limited to the embodiments described herein.

[0058] Preparation Example

[0059] Preparation Example 1: 25% Tetrazolylpyrrolidone·Formula I Compound Suspension (3:2)

[0060] By weight percentage, 15% tetrazolium pyrrolidone, 10% compound of formula I, 1% sodium lignin sulfonate, 2% phenethylphenol polyether phosphate, 1% polycarboxylate, 1% magnesium aluminum silicate, 0.2% xanthan gum, 5% propylene glycol, 0.2% sodium phenylate, 0.4% silicone oil, and deionized water to make up the balance;

[0061] Preparation method: According to the formula ratio, the active ingredient tetrazolium pyrrolidone and the compound of formula I, a surfactant and other functional additives are placed in a reaction kettle in sequence, water is added and mixed evenly, and the suspension is obtained by high-speed shearing, wet sand grinding, and finally homogenization filtration.

[0062] Preparation Example 2: 36% Tetrazolylpyramidate·Formula I compound water dispersible granules (3:1)

[0063] By weight percentage, 27% tetrazolium pyrrolidone, 9% compound of formula I, 8% sodium lignin sulfonate, 4% sodium naphthalene sulfonate, 5% calcium dodecylbenzene sulfonate, 8% ammonium sulfate, and kaolin makes up the balance;

[0064] Preparation method: According to the formula ratio, the active ingredient tetrazolium pyridine and the compound of formula I are added to a carrier, and a surfactant and other functional additives are added thereto, mixed, and then jet-milled. 10-25% of water is added, and then kneaded, granulated, dried, and sieved to obtain a water-dispersible granule product; or the pulverized powder is sprayed with water in a boiling granulator, granulated, dried, and then sieved to obtain a water-dispersible granule product.

[0065] Preparation Example 3: 30% Tetrazolylpyramidate·Formula I Compound Wettable Powder (1:1)

[0066] By weight percentage, 15% tetrazolium pyrrolidone, 15% compound of formula I, 5% sodium dodecylbenzenesulfonate, 3% sodium ligninsulfonate, 4% dispersant NNO, 5% white carbon black, and kaolin make up the balance;

[0067] Preparation method: According to the formula ratio, the active ingredient tetrazolium pyrrolidone and the compound of formula I as well as the dispersant, wetting agent and filler are mixed, uniformly stirred in a stirred tank, and pulverized and mixed uniformly multiple times in a jet mill to prepare a wettable powder.

[0068] Preparation Example 4: 20% Tetrazolylpyrrolidone·Formula I Compound Suspension (3:1)

[0069] By weight percentage, 15% tetrazolium pyrrolidone, 5% compound of formula I, 2% isomeric alcohol polyoxyethylene ether, 1% fatty alcohol polyoxyethylene ether, 3% sodium lignin sulfonate, 3% alkyl aryl polyoxyethylene ether polyoxypropylene ether, 0.5% xanthan gum, 1% magnesium aluminum silicate, 5% propylene glycol, 0.2% sodium phenylate, 0.5% silicone oil, and deionized water to make up the balance;

[0070] Preparation method: Same as Preparation Example 1.

[0071] Preparation Example 5: 36% Tetrazolylpyramidate·Formula I compound water dispersible granules (1:5)

[0072] By weight percentage, 6% tetrazolium pyrrolidone, 30% compound of formula I, 6% naphthalenesulfonate formaldehyde condensate, 3% flavonoid powder BX, 5% sodium lignin sulfonate, 10% glucose, and starch make up the balance;

[0073] Preparation method: same as Preparation Example 2.

[0074] Preparation Example 6: 30% Tetrazolylpyramidate·Formula I Compound Wettable Powder (2:1)

[0075] By weight percentage, 20% tetrazolium pyrrolidone, 10% compound of formula I, 7% naphthalenesulfonate formaldehyde condensate, 5% sodium ligninsulfonate, 3% pulverized powder BX, 8% ammonium sulfate, and kaolin makes up the balance;

[0076] Preparation method: Same as Preparation Example 3.

[0077] Indoor activity test:

[0078] Example 1: Test on the combined effect of tetrazolium pyrazone and compound of formula I on potato late blight

[0079] Test basis: The test refers to NY / T 1156.2-2006 "Standard of the Agricultural Industry of the People's Republic of China for Indoor Bioassay Test of Pesticides - Fungicides Part 2: Test Plate Method for Inhibition of Pathogenic Fungal Mycelial Growth" and NY / T 1156.6-2006 "Standard of the Agricultural Industry of the People's Republic of China for Indoor Bioassay Test of Pesticides - Fungicides Part 6: Determination of the Combined Effect of Mixtures".

[0080] Test pathogen: Potato late blight fungus (Phytophthora infestans).

[0081] Test agents: 97% tetrazolium pyrazone technical, 97% technical of the compound of formula I, both of which were provided by the R&D center of Hailier Pharmaceutical Group.

[0082] Preparation: Dissolve the test stock drug in acetone, then dilute with a 0.1% Tween 80 solution. Prepare separate stock solutions and set the required concentrations based on the mixing purpose and drug activity. The final organic solvent content should not exceed 2%.

[0083] Melt the PDA culture medium in a microwave oven and cool it to about 50°C. Then, according to the principle of increasing the concentration from low to high, take 1 mL of the prepared drug solution and 9 mL of PDA culture medium and add them to a 9 cm diameter culture dish. Mix well to prepare drug-containing plates of the corresponding concentration.

[0084] The cultured pathogens were punched into a fungus cake using a 5 mm diameter puncher under sterile conditions. After the drug-containing culture medium solidified, the fungus cake was placed in the center of the culture medium. The culture dish was sealed with a sealing film and then placed in an incubator at 27°C for culture. A blank solution without drug was set as a blank control. Each treatment was repeated 4 times.

[0085] After culturing for 5 days, the diameter of the colonies was measured with a caliper in millimeters (mm). The diameter of each colony was measured vertically once using the cross-cross method, and the average value was taken.

[0086] The mycelial growth inhibition rate was calculated according to the following formula, and the unit was percentage (%), and the calculation result was rounded to two decimal places.

[0087] D=D1-D2

[0088] Where:

[0089] D——colony growth diameter;

[0090] D1 - colony diameter;

[0091] D2——diameter of mushroom cake.

[0092]

[0093] I——hyphae growth inhibition rate;

[0094] D0——blank control colony growth diameter;

[0095] D t ——The growth diameter of the colony after treatment with chemicals.

[0096] The co-toxicity coefficient (CTC value) of the mixture is calculated by the following formula:

[0097]

[0098] Where:

[0099] ATI - measured toxicity index of mixture;

[0100] S——EC of standard fungicide 50 , the unit is milligrams per liter (mg / L);

[0101] M——EC of the mixture 50 , the unit is milligrams per liter (mg / L).

[0102] TTI=TI A ×P A +TI B ×P B

[0103] Where:

[0104] TTI – Theoretical Toxicity Index of Mixtures;

[0105] TI A ——Agent toxicity index;

[0106] P A ——The percentage of agent A in the mixture, in percentage (%);

[0107] TI B ——Toxicity index of agent B;

[0108] P B ——The percentage of agent B in the mixture, in percentage (%).

[0109]

[0110] Where:

[0111] CTC – Co-toxicity coefficient;

[0112] ATI - measured toxicity index of mixture;

[0113] TTI - Theoretical Toxicity Index of Mixture.

[0114] A co-toxicity coefficient (CTC) of 120 or higher indicates a synergistic effect; a co-toxicity coefficient (CTC) of 80 or lower indicates an antagonistic effect; and a co-toxicity coefficient (CTC) of 80 or lower indicates an additive effect.

[0115] The DPS data processing software was used to calculate the test results and the toxicity regression equations and EC 50 The correlation coefficient was calculated, and the co-toxicity coefficient (CTC) of the two drugs in different ratios was calculated to screen out the optimal ratio of the test drugs.

[0116] The results of the indoor activity test are shown in the table below:

[0117] Table 1 Indoor activity test results of tetrazolium pyrrolidone and compound of formula I against potato late blight

[0118]

[0119] From the indoor activity test (see Table 1), the single agent of tetrazolium pyrrolidone and the compound of formula I is effective against potato late blight EC 50 The concentrations of tetrazolium pyrazone and the compound of formula I were 0.4118 mg / L and 0.2013 mg / L, respectively. Potato late blight was relatively sensitive to the compound of formula I. When tetrazolium pyrazone and the compound of formula I were mixed in a ratio of 1:20 to 30:1, the co-toxicity coefficient was greater than 120, showing a synergistic effect in preventing and controlling potato late blight.

[0120] Example 2: Test on the combined effect of tetrazolium pyrazone and compound of formula I on cucumber downy mildew

[0121] Test basis: The test was conducted with reference to the Agricultural Industry Standards of the People's Republic of China (NY / T 1156.7-2006 and NY / T1156.6-2006): "Guidelines for Indoor Bioassay Tests of Pesticides - Fungicides" Part 7 (Pot Method for Control of Cucumber Downy Mildew) and Part 6 (Determination of Combined Effects of Mixtures).

[0122] Test target: Cucumber downy mildew (Pseudoperonospora cubensis).

[0123] Test agents: 97% tetrazolium pyrazone technical, 97% technical of the compound of formula I, the above technicals were provided by the R&D center of Hailier Pharmaceutical Group.

[0124] Preparation of test materials: Select susceptible cucumber varieties (Xintai Mici) for potting and wait until the seedlings grow to 4 to 6 true leaves for use.

[0125] Preparation of pharmaceutical agents: Dissolve the two original drugs in acetone respectively, dilute with 0.1% Tween 80 aqueous solution, and set the required series of mass concentrations according to the activity of the pharmaceutical agents.

[0126] Chemical treatment: Spray the chemical evenly on the cucumber seedlings and let them dry naturally. A treatment without chemical was used as a blank control.

[0127] Inoculation and Culture: 24 hours after treatment, spray a sporangium suspension of cucumber downy mildew onto cucumber seedlings. Incubate in a high-humidity environment for 12 hours, then incubate at 20-24°C, 65-75% humidity, and a light intensity ratio of L:D = 12:12h. Five pots were used for each treatment, with two plants per pot.

[0128] Data investigation: Based on the graded investigation of the disease incidence of the blank control, the inoculated leaves were graded.

[0129] The following grading method is used:

[0130] Level 0: no lesions;

[0131] Level 1: The lesion area accounts for less than 5% of the whole leaf area;

[0132] Level 3: The lesion area accounts for 6% - 10% of the whole leaf area;

[0133] Level 5: The lesion area accounts for 11% - 25% of the whole leaf area;

[0134] Level 7: The lesion area accounts for 26% - 50% of the whole leaf area;

[0135] Level 9: The lesion area accounts for more than 50% of the whole leaf area.

[0136] Data statistics and analysis:

[0137] Based on the survey data, calculate the disease index and control effect of each treatment.

[0138] The disease index is calculated according to formula (1)

[0139]

[0140] In the formula:

[0141] X - disease index;

[0142] N i - number of diseased leaves at each level;

[0143] i - relative level value;

[0144] N - total number of leaves surveyed.

[0145] The control effect is calculated according to formula (2)

[0146]

[0147] In the formula:

[0148] P - control effect, unit is %;

[0149] CK - disease index of blank control;

[0150] PT - disease index of medicament treatment.

[0151] According to Sun Yunpei's co-toxicity coefficient method (CTC) to evaluate the synergistic effect of mixed pesticides, that is, CTC ≤ 80 is antagonistic effect, 80 < CTC < 120 is additive effect, CTC ≥ 120 is synergistic effect, and the co-toxicity coefficient (CTC) is calculated according to formula (3), formula (4), and formula (5).

[0152]

[0153] In the formula:

[0154] ATI - measured toxicity index of the mixture;

[0155] S——EC of standard agent 50 , the unit is milligrams per liter (mg / L);

[0156] M——EC of the mixture 50 , the unit is milligrams per liter (mg / L).

[0157] TTI=TI A ×P A +TI B ×P B ............................(4)

[0158] Where:

[0159] TTI – Theoretical Toxicity Index of the mixture;

[0160] TI A ——Toxicity index of agent A;

[0161] P A ——The percentage of agent A in the mixture, in percentage (%);

[0162] TI B ——Toxicity index of agent B;

[0163] P B ——The percentage of agent B in the mixture, in percentage (%).

[0164]

[0165] Where:

[0166] CTC – Co-toxicity coefficient;

[0167] ATI - measured toxicity index of mixture;

[0168] TTI - Theoretical Toxicity Index of Mixture.

[0169] The experiment used the DPS data processing system to process the data, establish the toxicity regression equation, and calculate the EC of the drug. 50 value and co-toxicity coefficient.

[0170] The results of the indoor combined action test are shown in the table below:

[0171] Table 2 Indoor activity test of tetrazolium pyrazone and fluazinam mixture against cucumber downy mildew

[0172]

[0173]

[0174] From the indoor activity test (see Table 2), the single agent of tetrazolium pyrrolidone and the compound of formula I is effective against cucumber downy mildew EC 50 The concentrations of tetrazolium pyraclostrobin and the compound of formula I were 12.7634 mg / L and 5.9529 mg / L, respectively. Cucumber downy mildew was more sensitive to the compound of formula I. The co-toxicity coefficients of tetrazolium pyraclostrobin and the compound of formula I were greater than 120 when mixed in a ratio of 1:10 to 10:1, showing a synergistic effect on the prevention and control of cucumber downy mildew.

[0175] Field efficacy trials

[0176] Example 3: Field efficacy test of a mixture of tetrazolium pyrazone and a compound of formula I for controlling potato late blight

[0177] Test basis: The test refers to GB / T 17980.34-2000 "Guidelines for field efficacy tests of pesticides (I) Part 34: Fungicides for control of potato late blight".

[0178] Test crops and varieties: Potato (Qinyu No. 30).

[0179] Target of prevention and control: potato late blight.

[0180] Test location and application time: Laixi City, Shandong Province, application time is mid-September 2019.

[0181] Experimental method: Each experimental plot is arranged in random blocks, with an area of ​​24m 2 , repeat 4 times.

[0182] Application method and frequency: In the early stage of potato late blight, conventional spraying method is used for application, and application is carried out once every 7 days after application, for a total of 3 times.

[0183] Survey Method: A baseline disease survey was conducted before the first application, followed by a control efficacy survey 10 days after the final application, for a total of two surveys. Samples were collected at five diagonal points in each plot, with three plants at each point. All leaves were surveyed, and the percentage of lesion area on each leaf to the total leaf area was used to grade and calculate the disease index and control efficacy.

[0184] Leaf grading standards:

[0185] Level 0: no lesions;

[0186] Level 1: The lesion area accounts for less than 5% of the entire leaf area;

[0187] Level 3: The lesion area accounts for 6% to 15% of the entire leaf area;

[0188] Level 5: The lesion area accounts for 16% to 25% of the entire leaf area;

[0189] Level 7: The lesion area accounts for 26% to 50% of the entire leaf area;

[0190] Level 9: The lesion area accounts for more than 50% of the entire leaf area.

[0191] The efficacy is calculated as follows:

[0192]

[0193]

[0194] The results of the field efficacy test are shown in the table below:

[0195] Table 3 Field efficacy test results of tetrazolium pyrazone and compound of formula I for preventing and controlling potato late blight

[0196]

[0197] Field efficacy results (see Table 3) show that under the same environmental conditions, the overall field efficacy of different treatments for controlling potato late blight ranged from 67.35% to 88.35% seven days after the last application of the pesticide. When the dosage of the active ingredient was reduced, the control efficacy of 25% tetrazolium pyridine suspension concentrate·compound of Formula I (3:2) against potato late blight was 88.35%, which was superior to the single-dose control (10% tetrazolium pyridine suspension concentrate and 500 g / L suspension concentrate of Formula I).

[0198] Example 4: Field efficacy test of a mixture of tetrazolium pyrazone and a compound of formula I for controlling cucumber downy mildew

[0199] Test basis: The test refers to GB / T 17980.26-2000 "Guidelines for field efficacy tests of pesticides (I) Part 26: Fungicides for the control of cucumber downy mildew".

[0200] Test crops and varieties: cucumber (Xintai Mici);

[0201] Target of prevention and control: cucumber downy mildew;

[0202] Test location and application time: Greenhouse in Nanpan Village, Shouguang City, Shandong Province. The application time was mid-March 2019.

[0203] Experimental method: Each experimental plot is arranged in random blocks, with an area of ​​20m 2 , repeat 4 times.

[0204] Application method and frequency: In the early stage of cucumber downy mildew, conventional spraying method is used for application, and then one more application is conducted 8 days after application, for a total of 2 applications.

[0205] Survey Method: A baseline disease prevalence survey was conducted before the first application, followed by another survey 7 days after the first application and 11 days after the second application. The efficacy of each treatment was calculated. Four random sites were selected per plot, with two plants surveyed at each site, and all leaves of each plant were examined.

[0206] Grading method (based on leaves):

[0207] Level 0: no lesions;

[0208] Level 1: The lesion area accounts for less than 5% of the entire leaf area;

[0209] Level 3: The lesion area accounts for 6-10% of the entire leaf area;

[0210] Level 5: The lesion area accounts for 11-25% of the entire leaf area;

[0211] Level 7: The lesion area accounts for 26-50% of the entire leaf area;

[0212] Level 9: The lesion area accounts for more than 50% of the entire leaf area.

[0213] The efficacy is calculated as follows:

[0214]

[0215]

[0216] The results of the field efficacy test are shown in the table below:

[0217] Table 4 Field efficacy test results of tetrazolium pyrazone and compound of formula I for controlling cucumber downy mildew

[0218]

[0219] Field efficacy results (see Table 4) show that under the same environmental conditions, the overall efficacy of different treatments against cucumber downy mildew ranged from 71.42% to 83.54% 7 days after the first application of the pesticide. 40 g / hm2 of 30% tetrazolium pyrazone·compound of formula I wettable powder (2:1) was sprayed. 2 、60g / hm 2 、80g / hm 2 The control effects of three different dosages on cucumber downy mildew were 81.18%, 82.75%, and 83.54%, respectively, which were better than the single-dose control (10% tetrazolium pyridine suspension and 500g / L suspension of formula I compound). The dosage was 80g / hm 2 Eleven days after the second application, the overall control effect of each treatment field was 73.86% to 88.29%, and 30% tetrazolium pyridine ester·Formula I compound wettable powder (2:1) was sprayed at 60g / hm 2, 90g / hm 2 、120g / hm 2 The control effects of three different dosages on cucumber downy mildew were 84.34%, 86.88% and 88.29% respectively.

[0220] The results of the above indoor and field tests showed that the combination of tetrazolium pyrazone and the compound of formula I in an appropriate ratio showed good control effects on cucumber downy mildew and potato late blight. In addition, during the test, the test concentrations of each agent were safe for cucumbers and potatoes and did not cause any phytotoxicity.

[0221] Therefore, the combination of tetrazolium pyrrolidone and the compound of formula I can alleviate the increasing trend of resistance to cucumber downy mildew and potato late blight year by year, improve the control effect of cucumber downy mildew and potato late blight, and extend the service life of the agent.

[0222] The above embodiments are merely exemplary implementations used to illustrate the principles of the invention. However, the invention is not limited thereto. Those skilled in the art may make various improvements and changes without departing from the essence of the invention, and these improvements and changes also fall within the scope of protection of the invention.

Claims

1. A bactericidal composition, characterized in that: The active ingredients of the fungicide composition are composed of tetrazolium pyrrolidone and a compound of formula I: (Formula I), the mass ratio of the tetrazolium pyrrolidone to the compound of Formula I is 1:20~30:

1.

2. The bactericidal composition according to claim 1, characterized in that The mass ratio of the tetrazolium pyrrolidone to the compound of formula I is 1:10 to 10:

1.

3. The bactericidal composition according to claim 1, characterized in that The total weight of the bactericidal composition is 100wt%, and the total weight of the active ingredient tetrazolium pyrrolidone and the compound of formula I accounts for 0.1% to 90% of the total weight of the bactericidal composition.

4. The bactericidal composition according to claim 3, characterized in that The total weight of the bactericidal composition is 100wt%, and the total weight of the active ingredient tetrazolium pyrrolidone and the compound of formula I accounts for 2% to 70% of the total weight of the bactericidal composition.

5. The bactericidal composition according to claim 1, characterized in that In addition to the active ingredients, the fungicide composition also includes agriculturally permitted auxiliary ingredients, and the auxiliary ingredients are selected from one or more of wetting agents, dispersants, emulsifiers, thickeners, disintegrants, antifreeze agents, defoaming agents, solvents, preservatives, stabilizers, synergists or carriers.

6. The bactericidal composition according to claim 1, characterized in that The bactericidal composition can be prepared in the form of water dispersible granules, wettable powders or suspensions.

7. Use of the fungicidal composition and / or its preparation according to any one of claims 1 to 6 in preventing and controlling plant diseases.

8. The use according to claim 7, characterized in that: The plant disease is caused by fungi belonging to the subphylum Mastigomycotina; the fungi belonging to the subphylum Mastigomycotina are Phytophthora infestans or Pseudocoperonospora cubana.

9. The use according to claim 7, characterized in that: The bactericidal composition and / or its preparation is applied to the pathogens to be controlled or their growth medium at an effective dose.

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